Photosalience and Thermal Phase Transitions of Azobenzene- and Crown Ether-Based Complexes in Polymorphic Crystals

Stimuli-responsive molecular crystals have attracted considerable attention as promising smart materials with applications in various fields such as sensing, actuation, and optoelectronics. Understanding the structure–mechanical property relationships, however, remains largely unexplored when it comes to functionalizing these organic crystals. Here, we report three polymorphic crystals (Forms A, B, and C) formed by the non-threaded complexation of a dibenzo[18]crown-6 (DB18C6) ether ring and an azobenzene-based ammonium cation, each exhibiting distinct thermal phase transitions, photoinduced deformations, and mechanical behavior. Structural changes on going from Form A to Form B and from Form C to Form B during heating and cooling, respectively, are observed by single-crystal X-ray crystallography. Form A shows photoinduced reversible bending, whereas Form B exhibits isotropic expansion. Form C displays uniaxial negative expansion with a remarkable increase of 44% in thickness under photoirradiation. Force measurements and nanoindentation reveal that the soft crystals of Form A with a low elastic modulus demonstrate a significant photoresponse, attributed to the non-threaded molecular structure, which permits flexibility of the azobenzene unit. This work represents a significant advance in the understanding of the correlation between structure–thermomechanical and structure–photomechanical properties necessary for the development of multi-stimulus-responsive materials with tailored properties.